title: Activating catalysts with mechanical force.
abstract: Homogeneously catalysed reactions can be 'switched on' by activating latent catalysts. Usually, activation is brought about by heat or an external chemical agent. However, activation of homogeneous catalysts with a mechanical trigger has not been demonstrated. Here, we introduce a general method to activate latent catalysts by mechanically breaking bonds between a metal and one of its ligands. We have found that silver(I) complexes of polymer-functionalized N-heterocyclic carbenes, which are latent organocatalysts, catalyse a transesterification reaction when exposed to ultrasound in solution. Furthermore, ultrasonic activation of a ruthenium biscarbene complex with appended polymer chains results in catalysis of olefin metathesis reactions. In each case, the catalytic activity results from ligand dissociation, brought about by transfer of mechanical forces from the polymeric substituents to the coordination bond. Mechanochemical catalyst activation has potential applications in transduction and amplification of mechanical signals, and mechanically initiated polymerizations hold promise as a novel repair mechanism in self-healing materials.
authors.affiliation: Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, 5600 MB Eindhoven, The Netherlands.
authors.forename: Alessio
authors.initials: A
authors.lastname: Piermattei
authors.forename: S
authors.initials: S
authors.lastname: Karthikeyan
authors.forename: Rint P
authors.initials: RP
authors.lastname: Sijbesma
mesh_terms: D000475:Alkenes / Q000737:chemistry; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry*; D008024:Ligands; D055595:Mechanical Phenomena; D008670:Metals / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives / Q000737:chemistry; D011108:Polymers / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry; D012834:Silver / Q000737:chemistry
chemical_list: D000475:Alkenes; D056831:Coordination Complexes; D008024:Ligands; D008670:Metals; D011108:Polymers; C030011:carbene; D012834:Silver; D012428:Ruthenium; D008697:Methane